A twofold interpenetrating 3D brick-wall MOF based on a new semi-rigid tridentate ligand: synthesis,structure, and selective CO2 adsorption

Journal of Porous Materials - Based on a new semi-rigid tridentate azole ligand, a porous metal–organic framework (MOF), {[Ni3(tmpa)2(bdc)3]·6DMF}n (1)...     

Hydrogen sulfide gas detection by Au-decorated ZnO nanotube: a computational study and comparison to experimental observations

Based on the experimental reports, Au-decoration on the ZnO nanostructures dramatically increases the electronic sensitivity to H₂S gas. In the current study, we computationally scrutinized the mechanism of Au-decoration on a ZnO nanotube (ZON) and the influence on its sensing behavior toward H₂S gas. The intrinsic ZON weakly interacted with the H₂S gas with an adsorption energy of ?11.2 kcal/mol. The interaction showed no effect on the HOMO–LUMO gap and conductivity of ZON. The predicted response of intrinsic ZON toward H₂S gas is 6.3, which increases to 78.1 by the Au-decoration at 298 K. The corresponding experimental values are about 5.0 and 80.0, indicating excellent agreement with our findings. We showed that the Au atom catalyzes the reaction 3O₂?+?2H₂S?→?2SO₂?+?2H₂O. Our calculated energy barrier (at 298 K) is about 12.3 kcal/mol for this reaction. The gap and electrical conductance Au-ZON largely changed by this reaction are attributed to the electron donation and back-donation processes. The obtained recovery time is about 1.35 ms for desorption of generated gases from the surface of the Au-ZON sensor.     

Hydrodynamics study of a fast liquid–liquid oxidation process with in situ gas production in microreactors

Hydrodynamics characteristics of a fast and highly exothermic liquid–liquid oxidation process with in situ gas production in microreactors were studied using a newly developed experimental method. In the adipic acid synthesis through the K/A oil (the mixture of cyclohexanol and cyclohexanone) oxidation with nitric acid, bubble generation modes were divided into four categories. The gas production became more intensive, unstable, even explosive with increasing the oil phase feed rate and the temperature. A novel automatic image processing method was developed to monitor the instantaneous velocity online by tracking the gas–liquid interface. The axial velocity at the same location was unstable due to the changing gas production rate. Furthermore, the actual residence time was obtained easily with being only 36% of the space–time minimally, beneficial for establishing accurate kinetics and mass transfer models with time participation. Finally, an empirical correlation was developed to predict the actual residence time under different conditions.     

Dual-phase rare-earth-zirconate high-entropy ceramics with glass-like thermal conductivity

A series of rare earth zirconates (RE₂Zr₂O₇) high-entropy ceramics with single- and dual-phase structure were prepared. Compared with La₂Zr₂O₇ and Yb₂Zr₂O₇, the smaller “rattling” ions (Yb³⁺, Er³⁺, Y³⁺) have been incorporated into pyrochlore lattice in (La_0.2Nd_0.2Y_0.2Er_0.2Yb_0.2)₂Zr₂O₇ (LNYEY) while larger ions (La³⁺, Nd³⁺, Sm³⁺, Eu³⁺) incorporated into fluorite lattice in (La_0.2Nd_0.2Sm_0.2Gd_0.2Yb_0.2)₂Zr₂O₇ (LNSGY). Due to high-entropy lattice distortion and resonant scattering derived from smaller ions Yb³⁺, Er³⁺, and Y³⁺, LNYEY shows a lower glass-like thermal conductivity (1.62-1.59 W m^-1 K^-1, 100-600℃) than LNSGY (1.74-1.75 W m^-1 K^-1, 100-600℃). Moreover, LNYEY and LNSGY exhibit enhanced Vickers’ hardness (LNYEY, H_v = 11.47 ± 0.41 GPa; LNSGY, H_v = 10.96 ± 0.26 GPa) and thermal expansion coefficients (LNYEY, 10.45 × 10^-6 K^-1, 1000℃; LNSGY, 11.02 × 10^-6 K^-1, 1000℃). These results indicate that dual-phase rare-earth-zirconate high-entropy ceramics could be desirable for thermal barrier coatings.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Ni1−xCoxSe2?C/ZnIn2S4 Hybrid Nanocages with Strong 2D/2D Hetero-Interface Interaction Enable Efficient H2-Releasing Photocatalysis

Designing a semiconductor-based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron-hole pairs is highly important for enhancing H₂ releasing photocatalysis. Here, a new class of Ni_1−xCo_xSe₂–C/ZnIn₂S₄ hierarchical nanocages with abundant and compact ZnIn₂S₄ nanosheets/Ni_1−xCo_xSe₂^ C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero-junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C, improving the separation and transfer of photo-generated electron-hole pairs. As a consequence, the distinctive Ni_1−xCo_xSe₂ C/ZnIn₂S₄ hierarchical nanocages without using additional noble-metal cocatalysts, display remarkable H₂-relaesing photocatalytic activity with a rate of 5.10 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn₂S₄ nanosheets and bare Ni_1−xCo_xSe₂ C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C 2D/2D hetero-interfaces can powerfully promote the separation of photo-generated charge carriers and the electrons transfer from ZnIn₂S₄ to Ni_1−xCo_xSe₂ C.     

Superior Low-Temperature Reversible Adhesion Based on Bio-Inspired Microfibrillar Adhesives Fabricated by Phenyl Containing Polydimethylsiloxane Elastomers

Gecko-inspired microfibrillar adhesives have achieved great progress in microstructure design and adhesion improvement over the past two decades. Space applications nowadays show great interest in this material for the characteristics of reversible adhesion and universal van der Waals interactions. However, the impact of harsh environment of space on the performance of microfibrillar adhesives, especially the extreme low temperature, is rarely addressed. Herein, microfibrillar adhesives fabricated by phenyl containing polydimethylsiloxane (p-PDMS) elastomers with superior low-temperature reversible adhesion is proposed. p-PDMS elastomers are synthesized through one-pot anionic ring-opening copolymerization, and the resulting elastomers become non-crystallizable with excellent low-temperature elasticity. Low-temperature adhesion tests demonstrate that the adhesion strength of microfibrillar adhesives fabricated by p-PDMS elastomers can be well maintained to as low as −120 °C. In contrast, the adhesion strength of pure PDMS microfibrillar adhesive reduces more than 50% below its crystallization temperature. The low-temperature cyclic adhesion tests further demonstrate that p-PDMS microfibrillar adhesives exhibit superior reversible adhesion compared to that of PDMS microfibrillar adhesives, owing to the sustainable conformal contact and even distribution of loads over repeated cycles. This study provides a new fabrication strategy for microfibrillar adhesives, and is beneficial for the practical application of microfibrillar adhesives.     

Organic Semiconducting Luminophores for Near-Infrared Afterglow,Chemiluminescence, and Bioluminescence Imaging

Optical imaging has played a pivotal role in deciphering in vivo bioinformatics but is limited by shallow penetration depth and poor imaging performance owing to interfering tissue autofluorescence induced by concurrent photoexcitation. The emergence of near-infrared (NIR) self-luminescence imaging independent of real-time irradiation has timely addressed these problems. There are two main kinds of self-luminescent agents, namely inorganic and organic luminophores. Inorganic luminophores usually suffer from long-term biotoxicity concerns resulting from potential heavy-metal ions leakage and nonbiodegradability, which hinders their further translational application. In contrast, organic luminophores, especially organic semiconducting luminophores (OSLs) with good biodegradable potential, tunable design, and outstanding optical properties, are preferred in biological applications. This review summarizes the recent progress of OSLs used in NIR afterglow, chemiluminescence, and bioluminescence imaging. Molecular manipulation and nanoengineering approaches of OSLs are discussed, with emphasis on strategies that can extend the emission wavelength from visible to NIR range and amplify luminescence signals. This review concludes with a discussion of current challenges and possible solutions of OSLs in the self-luminescence field.     

Enhanced electromagnetic microwave absorption of Fe/C/SiCN composite ceramics targeting in integrated structure and function

The Fe/C/SiCN composite ceramics were synthesized by polymer-derived method to obtain the integration of structure and functions. The electromagnetic waves (EMW) absorption properties at X and Ku bands were investigated. The addition of nano-sized Fe particles improved the magnetic loss and impedance matching, and the carbon nanotubes generated by the iron in-situ catalysis increased the internal relaxation polarization and interfacial polarization, which together improved the EMW absorption properties significantly. In particular, the Fe/C/SiCN-9 showed the optimum reflection loss (RL) of ?31.06 dB at 10.03 GHz with an effective absorption bandwidth (EAB, RL < ?10 dB) of 3.03 GHz at 2.51 mm, indicating the excellent EMW absorption properties of Fe/C/SiCN composite ceramics.     

Research advances in residual thermal stress of ceramic/metal brazes

Brazing, as a common method of bonding ceramic and metal, has been applied in microelectronics, aerospace, machinery and other domains extensively. The residual thermal stress in the brazed joint has direct effects on the mechanical properties of the joint, so how to control the generation of residual thermal stress has become the vital point. In this paper, the methods of reducing residual thermal stress in the brazing process in recent years are reviewed. The generation and effects of residual thermal stress in the brazed joint are introduced. Besides, the methods of detecting residual thermal stress are discussed, and different methods of reducing residual thermal stress in brazed joints are also analyzed. Finally, the future development directions of reducing residual thermal stress in the brazed joint are proposed.